Methods and compounds for making coatings, waveguides and other optical devices

ABSTRACT

A compound of the general formula R 1 MR 4 R 5 R 6  is provided where R 1  is a partially or fully fluorinated aryl, alkyl, alkenyl or alkynyl group, wherein M is selected from group 14 of the periodic table, wherein R 4 , R 5  and R 6  are independently an alkoxy group OR 3  or a halogen group X—except, a) where R 4 , R 5  and R 6  are each ethoxy, M is Si and R 1  is perfluorinated phenyl or perfluorinated vinyl; b) where R 4  is ethoxy, R 5  and R 6  are chlorine, M is Si, and R 1  is perfluorinated phenyl; or c) where R 4 , R 5  and R 6  are chlorine, M is Si, and R 1  is perfluorinated phenyl, perfluorinated methyl or perfluorinated vinyl. This compound formed can be further reacted to attach an additional organic R group, and/or hydrolyzed, alone or with one or more similar compounds, to form a material having a molecular weight of from 500 to 10,000, which material can be deposited on various substrates as a coating or deposited and patterned for a waveguide or other optical device components. Methods for making compounds of the general formula R 1 MR 4 R 5 R 6  are also disclosed.

BACKGROUND OF THE INVENTION

[0001] Growing internet and data communications are resulting in theneed for greater numbers and types of optical components withinexpanding optical networks. DWDM systems, or any system that utilizeslight to transmit information, utilize a variety of components forcreating, transmitting, manipulating and detecting light. Such opticaldevice components, also referred to as optoelectronic or photoniccomponents, often comprises at least a portion that is transmissive tolight at particular wavelengths. Fibers and planar light guides areexamples of passive light transmissive optical components within anoptical network. However, light manipulators (components that modify,filter, amplify, etc. light within the optical network) also often haveportions that are transmissive to light, as often do photodetectors andlight emittors.

[0002] Regardless of the type of optical device component, it is usuallydesirable that a material is used that is highly transmissive to thewavelengths used to transmit information through the optical network. Inaddition to low optical absorbance, the material should preferably havelow polarization dependent loss and have low birefringence andanisotropy, and low stress. It is also desirable that the material beeasy to deposit or form, preferably at a high deposition rate and at arelatively low temperature. Once deposited or formed, it is desirablethat the material can be easily patterned, preferably directly patternedwithout the need for photoresist and etching steps, and preferablypatterned with small feature sizes if needed. Once patterned, thematerial should preferably have low surface and/or sidewall roughness.The material should also preferably be hydrophobic to avoid uptake ofmoisture once installed and in use, and be stable with a relatively highglass transition temperature (not degrade or otherwise physically and/orchemically change upon further processing or when in use).

[0003] Often, current materials used for making optical devicecomponents have some, but not all, of these characteristics. Forexample, inorganic materials such as silica are relatively stable, haverelatively high glass transition temperatures have relatively lowoptical loss. However, silica materials often require higher depositiontemperatures (limiting substrates and components on the substrates) andhave lower deposition rates and cannot be directly patterned. Organicmaterials such as polymers can be deposited at lower temperatures and athigher deposition rates, but are relatively unstable and have lowerglass transition temperatures. What are needed are materials for opticaldevice components that have a larger number of the preferredcharacteristics set forth above.

SUMMARY OF THE INVENTION

[0004] A compound of the general formula R¹MR⁴R⁵R⁶ is provided where R¹is a partially or fully fluorinated aryl, alkyl alkenyl or alkynylgroup, wherein M is selected from group 14 of the periodic table,wherein R⁴, R⁵ and R⁶ are independently an alkoxy group OR³ or a halogengroup X—except, a) where R⁴, R⁵ and R⁶ are each ethoxy, M is Si and R¹is perfluorinated phenyl or perfluorinated vinyl; b) where R⁴ is ethoxy,R⁵ and R⁶ are chlorine, M is Si, and R¹ is perfluorinated phenyl; or c)where R⁴, R⁵ and R⁶ are chlorine, M is Si, and R¹ is perfluorinatedphenyl, perfluorinated methyl or perfluorinated vinyl. This compoundformed can be further reacted to attach an additional organic R group,and/or hydrolyzed, alone or with one or more similar compounds, to forma material having a molecular weight of from 500 to 10,000, whichmaterial can be deposited on various substrates as a coating ordeposited and patterned for a waveguide or other optical devicecomponents.

DESCRIPTION OF THE PREFERRED EMBODIMENTS COMPOUNDS

[0005] In the present invention, compounds are made that can behydrolyzed and condensed (alone or with one or more other compounds)into a material having a molecular weight of from 500 to 10,000(preferably from 1,000 to 3,000), which material can be deposited byspin-on, spray coating, dip coating, or the like. Such compounds arepreferably partially or fully fluorinated, though not necessarily so inall embodiments. The compounds will preferably have an element Mselected from groups 3-6 or 13-16 of the periodic table, which elementis preferably tri-, tetra- or penta-valent, and more preferablytetravalent, such as those elements selected from group 14 of theperiodic table. Connected to this element M are from three to fivesubstituents, wherein from one to three of these substituents areorganic groups to be discussed further below, with the remainder being ahalogen or an alkoxy group.

Compound Example I

[0006] In one embodiment of the invention, a compound is provided of thegeneral formula: R¹MOR³ ₃, where R¹ is any partially or fullyfluorinated organic group (preferably a partially or fully fluorinatedaryl, alkenyl, alkynyl or alkyl group), where M is an element selectedfrom column 14 of the periodic table, and where OR³ is an alkoxygroup—except where M is Si, R¹ is perfluorinated phenyl orperfluorinated vinyl, and OR³ is ethoxy, which, though not novel per se,can be part of one of the novel methods of the invention as will bediscussed further below. R¹ can have an inorganic component, though ifso, a portion should preferably be a partially or fully fluorinatedorganic component. In a more preferred example of this embodiment, R¹comprises a double bond that is capable of physical alteration ordegradation in the presence of an electron beam, or electromagneticradiation and a photoinitiator (or sensitizer, photoacid or thermalinitiator—to be discussed further below). In this example, R¹ could bean alkenyl group such as a vinyl group, or could be an epoxy or acrylategroup, that is preferably partially or fully fluorinated. Such a group,as will be discussed further herein, can allow for crosslinking uponapplication of an electron beam or preferably electromagnetic radiation(e.g. directing ultraviolet light through a mask with the materialcomprising a photoinitiator). In the alternative, R¹ could be an organicgroup that is (or a hybrid organic-inorganic group that comprises) asingle or multi ring structure (an “aryl group”) or an alkyl group ofany length, such as from 1 to 14 carbon atoms or longer (preferably4-10)—the alkyl group capable of being a straight or branched chain. IfR¹ is a ring structure, or a carbon chain of sufficient length (e.g. 4(or 5) or more carbons), then such an R¹ group can provide bulk to thefinal material once hydrolyzed, condensed and deposited on a substrate.If R¹ is a ring structure, whether single ring or multi ring, it canhave substituents thereon, fluorinated, though not necessarily, such asalkyl or alkenyl substituents (preferably from 1 to 5 carbons), andwhere the substituents on the ring structure can be at from 1 to 3locations around the ring. R¹ can be a 4 to 8 sided ring structure(preferably 5 or 6 sided) which ring structure could comprise N or O. R1could comprise nitrogen, or R¹ can also have an oxygen component, suchas a carboxylate group (e.g. acrylate, butenecarboxylate,propenecarboxylate, etc.).

[0007] In the example above, in R¹MOR³ ₃, M can be a tetravalent elementfrom column 14 of the periodic table (e.g. Si or Ge), or a tetravalentelement from column 16—e.g. Se (or a tetravalent early transitionmetal—such as titanium or zirconium). Also, OR³ is an alkoxy group,though preferably one having from 1 to 4 carbon atoms (longer alkoxygroups can be used, but are more expensive). Specific examples include:

Compound Example II

[0008] In yet another embodiment of the invention, a compound isprovided of the general formula: R¹MOR³ ₂X, where R¹ is any partially orfully fluorinated organic group (preferably a partially or fullyfluorinated aryl, alkenyl, alkynyl or alkyl group) as set forth above,where M is an element selected from group 14 of the periodic table asmentioned above, where X is a halogen, and where OR³ is an alkoxy groupas above. X in this example is preferably F, Cl, Br or I, and morepreferably Cl or Br. Specific examples of compounds within this categoryinclude

Compound Example III

[0009] In another embodiment of the invention, a compound is provided ofthe general formula: R¹MX₂OR³, where R¹ is any partially or fullyfluorinated organic group (preferably a partially or fully fluorinatedaryl, alkenyl, alkynyl or alkyl group) as set forth above, where M is anelement selected from group 14 of the periodic table as mentioned above,where OR³ is an alkoxy group as above, and where X is a halogen asabove—Except where M is Si, R¹ is perfluorinated phenyl, X is Cl, andOR³ is ethoxy, which, though not novel per se, is novel when used aspart of the methods of the invention as will be discussed further below.Specific examples within this category include

Compound Example IV

[0010] In a further embodiment of the invention, a compound is providedof the general formula: R¹MX₃, where R¹ is any partially or fullyfluorinated organic group (preferably a partially or filly fluorinatedaryl, alkenyl, alkynyl or alkyl group) as set forth above, where M is anelement selected from group 14 of the periodic table as mentioned above,and where X is a halogen as above—Except where M is Si, R¹ isperfluorinated phenyl, perfluorinated methyl or perfluorinated vinyl,and X is Cl, which, though not novel per se, are novel when used as partof the methods of the invention as will be discussed further below. (IfM is Si and X is Cl, some of these novel trichlorosilanes could be usedfor forming self assembled monolayers for making a surface hydrophobic,preferably by application in the vapor phase to a surface made ofsilicon and having OH end groups and moisture.) Specific examples withinthis category include

Compound Example V

[0011] In yet another embodiment of the invention, a compound isprovided of the general formula: R¹R²MOR³ ₂, where R¹ is any partiallyor fully fluorinated organic group (preferably a partially or fillyfluorinated aryl, alkenyl, alkynyl or alkyl group) as set forth abovewith respect to R¹, R² is any partially or fully fluorinated organicgroup (preferably a partially or fully fluorinated aryl, alkenyl,alkynyl or alkyl group) as set forth above with respect to R¹, or anysuch organic groups nonfluorinated, and where R¹ and R² are the same ordifferent from each other, where M is an element selected from group 14of the periodic table as mentioned above, and where OR³ is an alkoxygroup as above—except where M is Si, OR³ is ethoxy and R¹ and R² areperfluorinated phenyl groups, which compound is not novel per se, but isnovel when used as part of the methods of the invention as set forthbelow. Specific examples within this category include:

Compound Example VI

[0012] In another embodiment of the invention, a compound is provided ofthe general formula: R¹R²MXOR³, where R¹ is any partially or fullyfluorinated organic group (preferably a partially or fully fluorinatedaryl, alkenyl, alkynyl or alkyl group) as set forth above with respectto R¹, R² is any partially or fully fluorinated organic group(preferably a partially or fully fluorinated aryl, alkenyl, alkynyl oralkyl group) as set forth above with respect to R¹, or any such organicgroups nonfluorinated, and where R¹ and R² are the same or differentfrom each other, where M is an element selected from group 14 of theperiodic table as mentioned above, where OR³ is an alkoxy group asabove, and where X is a halogen. R¹ and R² can be the same or differentfrom each other. Specific examples within this category include:

Compound Example VII

[0013] In a further embodiment of the invention, a compound is providedof the general formula: R¹ R²MX₂, where R¹ is any partially or fullyfluorinated organic group (preferably a partially or fully fluorinatedaryl, alkenyl, alkynyl or alkyl group) as set forth above with respectto R¹, R² is any partially or fully fluorinated organic group(preferably a partially or fully fluorinated aryl, alkenyl, alkynyl oralkyl group) as set forth above with respect to R¹, or any such organicgroups nonfluorinated, and where R¹ and R² are the same or differentfrom each other, where M is an element selected from group 14 of theperiodic table as mentioned above, and where X is a halogen asabove—Except where M is Si, R¹ and R² are perfluorinated phenyl, and Xis Cl, which, though not novel per se, is novel when used as part of themethods of the invention as will be discussed further below. Specificexamples within this category include:

[0014] As Compounds V-VII have two organic groups, they can be formed byvarious combinations of Methods A, B and/or C (described in furtherdetail below).

Compound VIII

[0015] In a further embodiment of the invention, a compound is providedof the general formula: R¹R² R³MOR³, where R¹, R² and R³ areindependently an aryl, alkenyl, alkynyl or alkyl group) as set forthabove with respect to R¹ and R², and where R¹, R² and R³ can each be thesame or different from each other (and preferably at least one of whereR¹, R² and R³ is partially or fully fluorinated), where M is preferablyan element selected from group 14 of the periodic table as above, andwhere OR³ is an alkoxy group as above. One example is

[0016] though the organic groups need not each be the same as in thisexample, and need not each be fluorinated (though preferably at leastone of the organic groups is fluorinated).

Compound IX

[0017] In another embodiment of the invention, a compound is provided ofthe general formula: R¹R² R³MX, where R¹, R² and R³ are independently anaryl, alkenyl, alkynyl or alkyl group) as set forth above with respectto R¹ and R², and where R¹, R² and R³ can each be the same or differentfrom each other (and preferably at least one of where R¹, R² and R³ ispartially or fully fluorinated), where M is preferably an elementselected from group 14 of the periodic table as above, and where X is ahalogen as above. One example is:

[0018] As Compounds VIII and IX have three organic groups, they can beformed by various combinations of Methods A, B and/or C (which methodsare described in further detail below).

[0019] Other Compounds:

[0020] Additional compounds within the scope of the invention includethose having the general formula R¹MHX₂ where R¹, M and X are as aboveand H is hydrogen. One example is:

[0021] Other examples, where the fluorinated phenyl group is replacedwith a substituted phenyl, fluorinated alkyl, vinyl, etc. are possible.

[0022] It should be noted that M in the compound formula examples aboveneed not be tetravalent. M can also have other valencies, thoughpreferably tri- or penta-valent. Examples would include early transitionmetals in group 3 or 5 of the periodic table (e.g. Y, V or Ta), orelements in columns 13 (column headed by B) or 15 (column headed by N),such as B, Al or As. In such situations, the compounds above would haveone fewer or one additional alkoxy (OR³), halogen (X) or an organicgroup (R¹ or R² independently from the other organic group(s)). Examplesinclude R¹MOR³X, R¹MOR³ ₂, R¹MX₂, R¹R²MX, R¹R²MOR³, where M is atrivalent early transition metal (or similar examples with fivesubstituents selected from R¹ and/or R² groups, as well as alkoxy andhalogen groups for pentavalent elements (including metalloids ortransition metals). Such compounds could have the formulaR1_(3−m)MOR3_(m), R1_(5−m)MOR3_(m), R2R1_(4−m)MOR3_(m) orR2R1_(4−m)MOR3_(m). If such tri- or penta-valent elements are used, sucha compound would preferably be hydrolyzed and condensed as a dopant,rather than as the main portion of the material at the time ofhydrolysis and condensation (likewise with non-silicon tetravalentelements that form compounds in accordance with the tetravalent examplesabove, such as germanium compounds).

[0023] It should also be noted that the structures illustrated above areexemplary only, as other ring structures (3 sided—e.g. epoxy, or 4 to 8sided—preferably 5 or 6 sided) are possible, which structures caninclude nitrogen or oxygen in or bound the ring. The aryl group can havefrom 1 to 3 substitutents, such as one or more methyl, ethyl, ally,vinyl or other substituents—that can be fluorinated or not. Also, carbonchain R groups can include oxygen (e.g. carboxylate) or nitrogen, orsulpher. If an alkyl group is bound to the silicon (or other M group),it can have from 1 to 4 carbons (e.g. a C2+straight or C3+branchedchain), or up to 14 carbons (or more)—if used as a bulk enhancing groupfor later hydrolysis and deposition, 4 or more carbons are preferable.These aryl groups can be fully or partially fluorinated, as can alkenylor alkynyl groups if used.

[0024] Methods of Making the Compounds for Later Hydrolysis andCondensation:

[0025] In a number of the following examples of methods within the scopeof the present invention, “M” is silicon, OR³ is ethoxy, and X is Cl.However, as noted above, other alkoxy groups could easily be used(methoxy, propoxy, etc.), and other group 3-5 or 13-16 elements could beused in place of silicon and other halogens in place of chlorine.Starting materials can vary from tetraethoxy silane, to ethoxy silaneshaving one or more organic groups bound to the silicon, to chorosilaneshaving one or more chlorine groups and/or one or more organic groups, aswell as starting materials having chlorine and alkoxy groups and withone or more organic groups. Any compound examples within Compounds I-IXabove could be used as starting materials—or could be intermediate orfinal compounds as will be seen below. For example,trifluorovinyltriethoxysilane could be a final compound resulting fromreacting a particular trifluorovinyl compound with tetraethoxysilane, ortrifluorovinylsilane could be a starting material that, when reactedwith a particular pentafluorophenyl compound, results inpentafluorophenyltrifluorovinyldiethoxysilane. As mentioned above, it isalso preferred that any organic groups that are part of the startingmaterial or are “added” by chemical reaction to become part of thecompound as set forth below, are partially or fully fluorinated (orfully or partially deuterated), though such is not necessary as willalso be seen below.

[0026] One example of a method of the present invention comprisesproviding a compound R¹ _(4−q) MOR³ _(q) where M is selected from group14 of the periodic table, OR³ is an alkoxy group, R¹ is an alkyl,alkenyl, aryl or alkynyl, and q is from 2 to 4; reacting the compound R¹_(4−q) MOR³ _(q) with either a) Mg and R²X² where X² is Cl, Br or I andR² is an alkyl alkenyl, aryl or alkynyl group, or b) reacting with R²X²where R² is an alkyl, alkenyl, aryl or alkynyl group and wherein R² isfully or partially fluorinated or deuterated and X¹ is an element fromgroup 1 of the periodic table; so as to replace one of the OR³ groups inR¹ _(4−q) MOR³ _(q) so as to form R¹ _(4−q) R²MOR³ _(q−1).

[0027] The starting material preferably has 1 or 2 (or no) organicgroups (R¹) bound to the group 14 element “M”, which organic groups mayor may not comprise fluorine, with the remaining groups bound to M beingalkoxy groups. An additional preferably fluorinated (partially of fully)organic group becomes bound to the group 14 element by one of a numberof reactions. One method (Method A) involves reacting the startingmaterial with magnesium and a compound having the desired organic group(R²) bound to a halogen X² (preferably Cl, Br or I)—namely R² X², whichreaction replaces one of the alkoxy groups with the organic group R². Inthe above example, a single alkoxy group is replaced, however, dependingupon the molar ratios of starting material to R²X² and Mg, more than onealkoxy group can be replaced with an R² organic group. In one example ofthe above, a tetraethoxysilane, MOR³ ₄ is reacted with a compound R²X²where R² is a preferably fluorinated alkyl, aryl, alkenyl or alkynylgroup and X² is preferably Br or I, so as to form R²MOR³ ₃. In anotherexample, R¹MOR³ ₃ is reacted with R²X² so as to form R¹R²MOR³ ₂. Thisgroup of reactions can be referred to as: reacting the starting materialR¹ _(4−q) MOR³ _(q) with R²X² where R² is a preferably fluorinatedalkyl, aryl, alkenyl or alkynyl group and X² is preferably Br or I, soas to form R¹ _(4−q) R²MOR³ _(q−1).

[0028] This method A can be described as a method comprising reacting acompound of the general formula R¹ _(4−m)MOR³ _(m), wherein m is aninteger from 2 to 4, OR³ is an alkoxy, and M is an element selected fromgroup 14 of the periodic table; with a compound of the general formulaR²X²+Mg, wherein X² is Br or I, where R¹ and R² are independentlyselected from alkyl, alkenyl, aryl or alkynyl, and wherein at least oneof R¹ and R² is partially or fully fluorinated, so as to make a compoundof the general formula R²MR¹ _(3−n)OR³ _(n), wherein n is an integerfrom 1 to 3.

[0029] An alternate to the above method (Method B) is to react the samestarting materials (R¹ _(4−q) MOR³ _(q)) with a compound R²X¹ where, asabove, R² is an alkyl, alkenyl, aryl or alkynyl group and wherein R² isfully or partially fluorinated or deuterated and X¹ is an element fromgroup 1 of the periodic table; so as to replace an OR³ group in R¹_(4−q) MOR³ _(q) to form R¹ _(4−q) R²MOR³ _(q−1). In this example, X¹ isan element from group 1 of the periodic table, and is preferably Na, Lior K (more preferably Na or Li). In one example of the above, atetraethoxysilane, MOR³ ₄ is reacted with a compound R²X¹ where R² is apreferably fluorinated alkyl, aryl, alkenyl or alkynyl group and X¹ ispreferably an element from group I of the periodic table, so as to formR²MOR³ ₃. In another example, R¹MOR³ ₃ is reacted with R²X¹ so as toform R¹R²MOR³ ₂.

[0030] This method B can be described as a method comprising reacting acompound of the general formula R1_(4−m)MOR3_(m) wherein m is an integerfrom 2 to 4, R1 is selected from alkyl, alkenyl, aryl, or alkyl, alkenylor aryl, and wherein R1 is nonfluorinated, or fully or partiallyfluorinated, OR3 is alkoxy, and M is an element selected from group 14of the periodic table; with a compound of the general formula R2M1,wherein R2 is selected from alkyl, alkenyl, aryl, alkynyl, and whereinR2 is at least partially fluorinated; and M1 is an element from group Iof the periodic table; so as to make a compound of the general formulaR1_(4−m)MOR3_(m−1)R2.

[0031] A modification (Method C) of the aforementioned (Method B), is toreact the starting material (R¹ _(4−q) MOR³ _(q)) with a halogen orhalogen compound so as to replace one or more of the OR³ groups with ahalogen group due to reaction with the halogen or halogen compound. Thehalogen or halogen compound can be any suitable material such ashydrobromic acid, thionylbromide, hydrochloric acid, chlorine, bromine,thionylchloride or sulfurylchloride and the like. Depending upon theratio of halogen or halogen compound to starting material (and otherparameters such as reaction time and/or temperature), one or more alkoxygroups can be replaced by a halogen group—though in most examples, asingle alkoxy group or all alkoxy groups will be replaced. If a singlealkoxy group is replaced, then the starting material R¹ _(4−q) MOR³ _(q)becomes R¹ _(4−q) MOR³ _(q−1)X³ where X³ is a halogen from the halogenor halogen compound reacted with the starting material (or simply beginwith starting material R¹ _(4−q) MOR³ _(q−1)X³). If all alkoxy groupsare replaced due to the reaction with the halogen or halogen compound,then the starting material R¹ _(4−q) MOR³ _(q) becomes R¹ _(4−q) MX³_(q). Then, as mentioned for Method B above, either starting material R¹_(4−q) MOR³ _(q−1)X³ or R¹ _(4−q) MX³ _(q) is reacted with a compoundR²X¹ where R² is a preferably fluorinated alkyl, aryl, alkenyl oralkynyl group and X¹ is preferably an element from group I of theperiodic table, so as to form R¹ _(4−q) R²MOR³ _(q−1), R¹ _(4−q)R²MX³_(q−1) (or even R¹ _(4−q)R² ₂ MX³ _(q−2) depending upon reactionconditions). A reaction with R¹ _(4−q) MOR³ _(q−1)X³ is preferred due togreater ease of control of the reaction.

[0032] This Method C can be described as a method comprising reacting acompound of the general formula X3MOR3₃, where X3 is a halogen, M is anelement selected from group 14 of the periodic table, and OR3 is alkoxy;with a compound of the general formula R1M1; where R1 is selected fromalkyl, alkenyl, aryl and alkynyl and wherein R1 is partially or fullyfluorinated; and Ml is an element from group I of the periodic table; soas to form a compound of the general formula R1MOR3₃.

[0033] Related Methods B and C can be described as a single methodcomprising reacting a compound of the general formulaR1_(4−m)MOR3_(m−1)X_(n) wherein m is an integer from 2 to 4, and n is aninteger from 0 to 2, R1 is selected from alkyl, alkenyl, aryl, or alkyl,alkenyl or aryl, and wherein R1 is nonfluorinated, or fully or partiallyfluorinated; OR3 is alkoxy, and M is an element selected from group 14of the periodic table; with a compound of the general formula R2M1,wherein R2 is selected from alkyl, alkenyl, aryl, alkynyl, and whereinR2 is at least partially fluorinated, and M1 is an element from group Iof the periodic table; so as to make a compound of the general formulaR2MR1_(4−m)OR3_(m−n)X_(n−1).

[0034] Of course, as will be seen below, the above starting materials inthe method examples set forth above are only examples, as many otherstarting materials could be used. For example, the starting materialcould be a halide rather than an alkoxide (e.g. a mono-, di- ortrichlorosilanes) or another material having both alkoxy and halogengroups on the group 14 element, along with 0, 1 or even 2 organic groups(alkyl alkenyl, aryl, alkynyl) also bound to the group 14 element.Though the methods of the invention preferably use starting materialshaving the group 14 element set forth above, many different combinationsof alkoxy groups, halogen groups, and organic groups (alkyl, alkenyl, .. . etc.) can be bound to the group 14 element. And, of course, suchstarting materials can be commercially available starting materials orcan be made from other available starting materials (in which case suchmaterials are intermediate compounds in the methods of the invention).

[0035] In addition, the methods of the invention include, it is withinthe scope of the invention, that a method for forming a final compoundcould include Methods A, B and/or C above. For example, one organicgroup, preferably fluorinated, could become bound to the group 14element M by Method A followed by binding a second organic group,preferably fluorinated, to the group 14 element M by Method B. Or,Method B could be performed first, followed by Method A—or Method Ccould be performed in combination with Methods A and/or B, etc. And, ofcourse, any particular reaction (binding of an organic group to M) couldbe performed only once by a particular reaction, or multiple times(binding of multiple organic groups, the same or different from eachother) by repeating the same reaction (a, b or c) multiple times. Manycombinations of these various reactions and starting materials arepossible. Furthermore, any of the methods or method combinations couldinclude any of a number of additional steps including preparation of thestarting material, replacing one or more alkoxy groups of the finalcompound with halogens, purifying the final compound, hydrolysis andcondensation of the final compound (as will be described further below),etc.

EXAMPLE 1 Making a Compound I via Method B

CF₂═CF—Cl+sec/tert-BuLi→CF₂═CF—Li+BuCl

CF₂═CF—Li+Si(OEt)₄→CF₂═CF—Si(OEt)₃+EtOLi

[0036] 200 ml of freshly distilled dry Et₂O is added to a 500 ml vessel(under an argon atmosphere). The vessel is cooled down to −80° C. and 15g (0.129 mol) of CF2═CFCl gas is bubbled to Et₂O. 100 ml (0.13 mol) ofsec-BuLi is added dropwise during three hours. The temperature of thesolution is kept below −60° C. all the time. The solution is stirred for15 minutes and 29 ml (27.08 g, 0.130 mol) of Si(OEt)₄ is added in smallportions. The solution is stirred for over night allowing it to warm upto room temperature. Formed red solution is filtered and evaporated todryness to result crude trifluorovinyltriethoxysilane, CF₂═CFSi(OEt)₃.

EXAMPLE 2 Making a Compound I via Method C

CF₂═CF—Li+ClSi(OEt)₃→CF₂═CF—Si(OEt)₃+LiCl

[0037] CF₂═CFSi(OEt)₃ is also formed when 30.80 g (0.155 mol) ClSi(OEt)₃in Et₂O is slowly added to solution of CF₂═CF—Li (0.155 mol, 13.633g,prepared in situ) in Et₂O at −78° C. Reaction mixture is stirredovernight allowing it slowly warm to room temperature. LiCl is removedby filtration and solution evaporated to dryness to result yellowliquid, crude trifluorovinyltriethoxysilane.

EXAMPLE 3 Making a Compound IV via Method B or C

[0038] Follow steps in Example 1 or 2 above, followed by

CF₂═CF—Si(OEt)₃+excess SOCl₂+py.HCl→CF₂═CF—SiCl₃+3 SO₂+3 EtCl

[0039] 24.4 g (0.100 mol) crude trifluorovinyltriethoxysilane, 44 mL(0.60 mol, 71.4 g) thionylchloride and 1.1 g (0.0045 mol) pyridiniumhydrochloride are refluxed and stirred for 24 h. Excess of SOCl₂ isevaporated and trifluorovinyltrichlorosilane

[0040] is purified by distillation.

EXAMPLE 4 Making a Compound I via Method A

C₇F₇Br+M +excess Si(OEt)₄→C₇F₇Si(OEt)₃

[0041] 250 g (0.8418 mol) heptafluorobromotoluene, 22.69 g (0.933 mol)magnesium powder, small amount of iodine (15 crystals) and 750 mL(3.3672 mol, 701.49 g) tetraethoxysilane are mixed together at roomtemperature and diethylether is added dropwise to the vigorously stirredsolution until an exothermic reaction is observed (˜250 mL). Afterstirring at room temperature for 16 h diethylether is evaporated. Anexcess of n-heptane (˜600 mL) is added to precipitate the magnesiumsalts. Solution is filtrated and evaporated to dryness. The residue isfractionally distilled under reduced pressure to yieldheptafluorotoluene-triethoxysilane.

EXAMPLE 5 Making a Compound IV via Method A

[0042] Follow the steps in Example 4, followed by

C₇F₇Si(OEt)₃+6 SOCl+py.HCl→C₇F₇SiCl₃  2.

[0043] where 114.1 g (0.300 mol) heptafluorotoluenetriethoxysilane, 131mL (1.800 mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol)pyridinium hydrochloride are refluxed and stirred for 16 h Excess ofSOCl₂ is evaporated and perfluorotoluenetrichlorosilane

[0044] isolated by vacuum-distillation.

EXAMPLE 6 Making a Compound III via Method A

[0045] Follow same steps as in Example 5, except isolate (by vacuumdistillation at the end), perfluorotoluenedichloroethoxysilane,CF₃—C₆F₄—Si(OEt)Cl₂

EXAMPLE 7 Making a Compound V from a Compound I or II via Method C

C₆F₅Si(OEt)₃+SOCl₂+py.HCl→C₆F₅Si(OEt)₂Cl+EtCl  1.

C₆F₅Si(OEt)₂Cl+CF₂═CFLi→C₆F₅(CF₂═CF)Si(OEt)₂  2.

C₆F₅(CF₂═CF)Si(OEt)₂+excess SOCl₂+py.HCl→C₆F₅(CF₂═CF)SiCl₂  3.

[0046] 152.0 g (0.460 mol) pentafluorophenyltriethoxysilane, 34 mL(0.460 mol, 54.724 g) thionylchloride and 6.910 g (0.0598 mol)pyridinium hydrochloride are refluxed and stirred for 18 h. Pyridiniumhydrochloride is precipitated at −78° C. and the solution is filtrated.Pentafluorophenylchlorodiethoxysilane

[0047] is isolated by vacuum distillation.

[0048] Then 49.712 g (0.155 mol) pentafluorophenylchlorodiethoxysilane,C₆F₅SiCl(OEt)₂, in Et₂O is slowly added to solution of CF₂═CF—Li (0.155mol, 13.633g, prepared in situ) in Et₂O at −78° C. Reaction mixture isstirred overnight while it will slowly warm to room temperature. LiCl isremoved by filtration and the product,pentafluorophenyltrifluorovinyldiethoxysilane,

[0049] purified by distillation.

EXAMPLE 8 Making a Compound VII from a Compound I or II via Method C

[0050] Follow the steps above for Example 7, and then

[0051] 12.1 g (0.0328 mol)pentafluorophenyltrifluorovinyldiethoxysilane, 12 mL (0.1638 mol. 19.487g) thionylchloride and 0.50 g (0.0043 mol) pyridinium hydrochloride arerefluxed and stirred for 24 h. Excess of SOCl₂ is evaporated and residueis fractionally distilled under reduced pressure to yield a mixture of80% pentafluorophenyltrifluorovinyldichlorosilane.

EXAMPLE 9 Making a Compound I via Method A

C₆F₅Br+Mg+2 Ge(OEt)₄→C₆F₅Ge(OEt)₃

[0052] 61.5 mL (0.4944 mol, 122.095 g) pentafluorobromobenzene, 13.22 g(0.5438 mol) magnesium powder and 250.00 g (0.9888 mol)tetraethoxygermane are mixed together at room temperature anddiethylether is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (˜400 mL). After stirring at 35° C.for 16 h the mixture is cooled to room temperature and diethyletherevaporated. An excess of n-heptane (˜400 mL) is added to precipitate themagnesium salts. Solution is filtrated and evaporated to dryness. Theresidue is fractionally distilled under reduced pressure to yieldpentafluorophenyl-triethoxygermane.

EXAMPLE 10 Making a Compound IV via Method A

[0053] Follow the steps in Example 9, then:

[0054] 50 g (0.133 mol) pentafluorophenyltriethoxygermane, 58 mL (0.80mol. 95.2 g) thionylchloride and 1.97 g (0.017 mol) pyridiniumhydrochloride are refluxed and stirred for 24 h. Excess of SOCl₂ isevaporated and pentafluorophenyltrichlorogermane isolated by vacuumdistillation.

EXAMPLE 11 Making a Compound I via Method A

C₁₀F₇Br+Mg+excess Si(OEt)₄→C₁₀F₇Si(OEt)₃

[0055] 166.5 g (0.50 mol) 2-bromoperfluoronaphthalene, 13.37 g (0.55mol) magnesium powder and 448.0 mL (2.00 mol, 416.659 g)tetraethoxysilane are mixed together at room temperature anddiethylether is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (˜200 mL). After stirring at 35° C.for 16 h the mixture is cooled to room temperature and diethyletherevaporated. An excess of n-heptane (˜400 mL) is added to precipitate themagnesium salts. Solution is filtrated and evaporated to dryness. Theresidue is fractionally distilled under reduced pressure to yieldperfluoronaphthalenetriethoxysilane.

EXAMPLE 12 Making a Compound IV via Method A

[0056] Follow the steps in Example 11, then

[0057] 100 g (0.240 mol) perfluoronaphthalenetriethoxysilane, 105.2 mL(1.442 mol, 171.55 g) thionylchloride and 3.54 g (0.0306 mol) pyridiniumhydrochloride are refluxed and stirred for 24 h. Excess of SOCl₂ isevaporated and perfluoronaphthalenetrichlorosilane isolated by vacuumdistillation.

EXAMPLE 13 Making Compound V via Method A

C₆F₅Br+Mg+4 MeSi(OMe)₃→C₆F₅(Me)Si(OMe)₂

[0058] 57.9 mL (0.465 mol. 114.726 g) bromopentafluorobenzene, 12.42 g(0.511 mol) magnesium powder and 265 mL (1.858 mol, 253.128 g)methyltrimethoxysilane are mixed together at room temperature anddiethylether is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (˜320 mL). After stirring at 45° C.for 16 h the mixture is cooled to room temperature and diethyletherevaporated. An excess of n-heptane (˜300 mL) is added to precipitate themagnesium salts. Solution is filtrated and evaporated to dryness. Theresidue, methyl(pentafluorophenyl)dimethoxysilane, is used withoutfurther purification.

EXAMPLE 14 Making Compound VII via Method A

[0059] Follow steps in Example 13, then

[0060] 81.68 g (0.300 mol) methyl(pentafluorophenyl)dimethoxysilane, 109mL (1.50 mol, 178.4 g) thionylchloride and 3.69 g (0.0319 mol)pyridinium hydrochloride are refluxed and stirred for 16 h. Excess ofSOCl₂ is evaporated and methyl(pentafluorophenyl)dichlorosilane isolatedby vacuum-distillation.

EXAMPLE 15 Making a Compound V via Method A

2 C₆F₅Br+2 Mg+Si(OEt)₄→(C₆F₅)₂Si(OEt)₂

[0061] 265.2 mL (1.95 mol, 525.353 g) bromopentafluorobenzene, 52.11 g(2.144 mol) magnesium powder and 216 mL (0.975 mol. 203.025 g)tetraethoxysilane are mixed together at room temperature anddiethylether is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (˜240 mL). The solution is stirredfor 30 minutes after which additional 90 mL of Et₂O is carefully added.After stirring at 35° C. for 16 h the mixture is cooled to roomtemperature and diethylether evaporated. An excess of n-heptane (˜600mL) is added to precipitate the magnesium salts. Solution is filtratedand evaporated to dryness. The residue is fractionally distilled underreduced pressure to yield di(pentafluorophenyl)diethoxysilane.

EXAMPLE 16 Making a Compound V via Method C

C₆F₅Cl+sec-BuLi→C₆F₅Li+sec-BuCl

C₆F₅Li+C₆F₅Si(OEt)₂Cl→(C₆F₅)₂Si(OEt)₂+LiCl

[0062] 39.52 g (0.195 mol) chloropentafluorobenzene is weighed to a 1000mL vessel and 250 mL Et₂O is added. The vessel is cooled down to −70° C.and 150 mL (0.195 mol) of sec-BuLi (1.3 M) is added dropwise during onehour. The temperature of the solution is kept below −50° C. all thetime. The solution is stirred for 30 minutes and 62.54 g (0.195 mol) ofdiethoxychloropentafluorophenylsilane in Et₂O (100 mL) is added in smallportions. The solution is stirred for over night allowing it to warm upto room temperature. Formed clear solution is filtered and evaporated todryness to result di(pentafluorophenyl)diethoxysilane, (C₆F₅)₂Si(OEt)₂.

EXAMPLE 17 Making a Compound VII via Method A or C

[0063] Follow the steps in Example 15 or Example 16, then:

(C₆F₅)₂Si(OEt)₂+SOCl₂+py.HCl→(C₆F₅)₂SiCl₂

[0064] 180.93 g (0.400 mol) di(pentafluorophenyl)diethoxysilane, 146 mL(2.00 mol, 237.9 g) thionylchloride and 4.92 g (0.0426 mol) pyridiniumhydrochloride are refluxed and stirred for 16 h. Excess of SOCl₂ isevaporated and di(pentafluorophenyl)dichlorosilane isolated byvacuum-distillation.

EXAMPLE 18 Making an “Other Compound” via Method A

C₆F₅MgBr+HSiCl₃→C₆F₅(H)SiCl₂

[0065] 600.0 mL (0.300 mol) pentafluorophenyl magnesiumbromide (0.5 Msol. in Et₂O) is added dropwise to a solution of 30.3 mL (0.300 mol,40.635 g) HSiCl₃ in Et₂O at −70° C. Reaction mixture is allowed to warmslowly to room temperature by stirring overnight. Diethylether isevaporated and an excess of n-heptane (−200 mL) is added to precipitatethe magnesium salts. Solution is filtrated and evaporated to dryness.The residue, pentafluorophenyldichlorosilane, is purified by fractionaldistillation.

EXAMPLE 19 Making a Compound I via Method C

CH≡C—Na+ClSi(OEt)₃→CH≡C—Si(OEt)₃+NaCl

[0066] 79.49 g (0.400 mol) ClSi(OEt)₃ in Et₂O is slowly added to aslurry of CH≡C—Na (0.400 mol, 19.208 g) in Xylene/light mineral oil at−78° C. Reaction mixture is stirred overnight allowing it slowly warm toroom temperature. NaCl is removed by filtration and solution evaporatedto dryness to result acetylenetriethoxysilane.

EXAMPLE 20 Making a Compound VII via Method A

1. C₆F₅Br+Mg+CH₂═CH—Si(OEt)₃→C₆F₅(CH₂═CH)Si(OEt)₂

2. C₆F₅(CH₂═CH)Si(OEt)₂+SOCl₂+py.HCl→C₆F₅(CH₂═CH)SiCl₂

[0067] 100 mL (0.8021 mol, 198.088 g) pentafluorobromobenzene, 24.90 g(1.024 mol) magnesium powder and 670 mL (3.2084 mol, 610.623 g)vinyltriethoxysilane are mixed together at room temperature and Et₂O isadded dropwise to the vigorously stirred solution until an exothermicreaction is observed (˜400 mL). After stirring at 35° C. for 16 h themixture is cooled to room temperature and diethylether evaporated. Anexcess of n-heptane (˜500 mL) is added to precipitate the magnesiumsalts. Solution is filtrated and evaporated to dryness. The residue isfractionally distilled under reduced pressure to yieldpentafluorophenylvinyldiethoxysilane.

[0068] 120.275 g (0.3914 mol) pentafluorophenylvinyldiethoxysilane, 143mL (1.9571 mol, 232.833 g) thionylchloride and 5.880 g (0.0509 mol)pyridinium hydrochloride are refluxed and stirred for 24 h. Excess ofSOCl₂ is evaporated and pentafluorophenylvinyldichlorosilane

[0069] isolated by vacuum distillation.

EXAMPLE 21 Making a Compound I from Method B

CH₂═CH—C(═O)—O—Na+ClSi(OEt)₃→CH₂═CH—C(═O)—O—Si(OEt)₃+NaCl

[0070] 6.123 g (0.0651 mol) sodium acrylate is dissolved to 25 mL TMFand cooled to −70° C. 12.8 mL (0.0651 mol, 12.938 g)chlorotriethoxysilane in THF (15 mL) is added dropwise to reactionsolution. The solution is stirred for over night allowing it to warm upto room temperature. NaCl is removed by filtration and solutionevaporated to dryness to result clear liquid, acryltriethoxysilane.

EXAMPLE 22 Making a Compound II

CF₃—(CF₂)₇—CH₂—CH₂—Si(OEt)₃+SOCl₂+py.HCl→CF₃—(CF₂)₇—CH₂—CH₂—Si(OEt)₂Cl

[0071] 183.11 g (0.300 mol) 1H,1H,2H,2H-Perfluorodecyltriethoxysilane,22 mL (0.300 mol, 35.69 g) thionylchloride and 4.51 g (0.039 mol)pyridinium hydrochloride are refluxed and stirred for 16 h. Excess ofSOCl₂ is evaporated and 1H,1H,2H,2H-Perfluorodecylchlorodi(ethoxy)silaneisolated by vacuum-distillation.

[0072] Though this example is not using Methods A, B or C, method Ccould be used to add a second organic group (replacing the Cl group), orMethods A and B could be used replace an ethoxy group in the startingmaterial with an additional organic group. Also, the starting materialcould be made by Methods A, B or C (starting earlier with atetraethoxysilane and reacting as in the other examples herein).

EXAMPLE 23 Making a Compound I via Method A

C₈F₁₇Br+Mg+excess Si(OEt)₄→C₈F₁₇Si(OEt)₃

C₈F₁₇Si(OEt)₃+excess SOCl₂+py.HCl→C₈F₁₇SiCl₃

[0073] 250 g (0.501 mol) 1-Bromoperfluorooctane (or 273.5 g, 0.501 mol1-Iodoperfluorooctane), 13.39 g (0.551 mol) magnesium powder, smallamount of iodine (15 crystals) and 363 mL (2.004 mol, 339.00 g)tetraethoxysilane are mixed together at room temperature anddiethylether is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (˜200 mL). After stirring at roomtemperature for 16 h diethylether is evaporated. An excess of n-heptane(˜400 mL) is added to precipitate the magnesium salts. Solution isfiltrated and evaporated to dryness. The residue is fractionallydistilled under reduced pressure to yield perfluorooctyltriethoxysilane.

EXAMPLE 24 Making a Compound IV via Method A

[0074] Follow the steps in Example 23, then

[0075] 174.7 g (0.300 mol) perfluorooctyltriethoxysilane, 131 mL (1.800mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol) pyridiniumhydrochloride are refluxed and stirred for 16 h. Excess of SOCl₂ isevaporated and perfluorooctyltrichlorosilane isolated byvacuum-distillation.

EXAMPLE 25 Making a Compound I via Method A

CF₂═CF—O—CF₂—CF₂—Br+Mg+excess Si(OEt)₄→CF₂═CF—O—CF₂—CF₂—Si(OEt)₃

[0076] 138.47 g (0.500 mol) 2-Bromotetrafluoroethyl trifluorovinylether, 13.37 g (0.550 mol) magnesium powder, small amount of iodine (10crystals) and 362 mL (2.000 mol, 338.33 g) tetraethoxysilane are mixedtogether at room temperature and diethylether is added dropwise to thevigorously stirred solution until an exothermic reaction is observed(˜200 mL). After stirring at room temperature for 16 h diethylether isevaporated. An excess of n-heptane (˜400 mL) is added to precipitate themagnesium salts. Solution is filtrated and evaporated to dryness. Theresidue is fractionally distilled under reduced pressure to yieldtetrafluoroethyl trifluorovinyl ether triethoxysilane.

EXAMPLE 26 Making a Compound IV via Method A

[0077] Follow steps in Example 25, followed by

[0078] 108.1 g (0.300 mol) tetrafluoroethyl trifluorovinyl ethertriethoxysilane, 131 mL (1.800 mol, 214.1 g) thionylchloride and 4.51 g(0.039 mol) pyridinium hydrochloride are refluxed and stirred for 16 h.Excess of SOCl₂ is evaporated and tetrafluoroethyl trifluorovinyl ethertrichlorosilane is isolated by vacuum-distillation.

EXAMPLE 27 Making a Compound I via Method B

CF≡C—Li+ClSi(OEt)₃→CF≡C—Si(OEt)₃+LiCl

[0079] 30.80 g (0.155 mol) ClSi(OEt)₃ in Et₂O is slowly added tosolution of CF≡C—Li (0.155 mol, 7.744 g, prepared in situ) in Et₂O at−78° C. Reaction mixture is stirred overnight allowing it slowly warm toroom temperature. LiCl is removed by filtration and solution evaporatedto dryness to result fluoroacetylenetriethoxysilane.

EXAMPLE 28 Making a Compound VIII via Method C

(C₆F₅)₂Si(OEt)₂+SOCl₂→(C₆F₅)₂Si(OEt)Cl+EtCl+SO₂

C₆F₅Li+(C₆F₅)₂Si(OEt)Cl→(C₆F₅)₃SiOEt+LiCl

(C₆F₅)₃SiOEt+SOCl₂→(C₆F₅)₃SiCl+EtCl+SO₂

[0080] 180.93 g (0.400 mol) di(pentafluorophenyl)diethoxysilane, 29 mL(0.400 mol, 47.6 g) thionylchloride and 4.92 g (0.0426 mol) pyridiniumhydrochloride are refluxed and stirred for 16 h. Unreacted SOCl₂ isevaporated and di(pentafluorophenyl)chloroethoxysilane isolated byvacuum distillation.

[0081] 88.54 g (0.200 mol) of dipentafluorophenyl)chloroethoxysilane inEt₂O is slowly added to solution of C₆F₅—Li (0.200 mol, 34.80 g,prepared in situ) in Et₂O at −78° C. The solution is stirred for overnight allowing it to warm up to room temperature. Formed clear solutionis filtered and evaporated to dryness to resulttri(pentafluorophenyl)ethoxysilane, (C₆F₅)₃SiOEt.

EXAMPLE 29 Making a Compound IX via Method C

[0082] Follow steps in Example 28, followed by

[0083] 114.86 g (0.200 mol) tri(pentafluorophenyl)ethoxysilane, 14.6 mL(0.200 mol. 23.8 g) thionylchloride and 2.46 g (0.0213 mol) pyridiniumhydrochloride are refluxed and stirred for 16 h. Unreacted SOCl₂ isevaporated and tri(pentafluorophenyl)chlorosilane isolated byvacuum-distillation.

[0084] In addition to altering the organic groups in the above examples,it is of course also possible to use other reagents in the methodsabove. For example, in place of diethyl ether, other solvents such asTHF could be used. In place of n-heptane (in Method A) other non polarsolvents such as n-hexane could be used. And in place of thionylchloride (for replacing one or more alkoxy groups with a halogen),chlorine, hydrochloric acid, hydrobromic acid, thionylbromide, chlorineor sulfurylchloride could be used. Also, the temperatures and times (andother process parameters) can be varied as desired. In one embodiment,it is preferred that the molar ratio of the starting material to R²X¹(Methods B or C) is 0.5:1 to 2:1—preferably 1:1. Also, the startingmaterial and R²X¹ are preferably mixed at a temperature less than −40 C.degrees, e.g. between −50 C. and −100 C. and warmed to a highertemperature over a period of four hours or more (this higher temperaturecan be room temperature or higher if desired)—or over a longer period oftime such as overnight.

[0085] As can be seen from the examples above, Methods B and C of theinvention involve reacting a first compound (having an M group selectedfrom group 14 of the periodic table, 0, 1 or 2 organic groups bound toM) with a second compound (having an element from group I of theperiodic table and a “new” organic group). As can also be seen from theabove, such a reaction can take place if the first compound has alkoxygroups bound to M or both alkoxy and halogen groups (0, 1 or 2 halogengroups) bound to M. Method C, as mentioned earlier, is a variation ofMethod B—and both methods can be viewed as comprising: reacting acompound of the general formula R¹ _(4−m)MOR³ _(m−n)X_(n), where R¹ isany nonfluorinated (including deuterated) or partially or fullyfluorinated organic group (preferably a partially or fully fluorinatedaryl, alkenyl, alkynyl or alkyl group) as set forth above, where M isselected from group 14 of the periodic table, where X is a halogen,where OR³ is an alkoxy group, where m 2 to 4 and n=0 to 2. R¹ _(4−m)MOR³_(m−n)X_(n) is reacted with R²X¹ where R² is selected from alkyl,alkenyl, aryl or alkynyl (and where R² is fluorinated (fully orpartially), and where X¹ is an element from group I of the periodictable. X¹ is preferably Na, Li or K, more preferably Na or Li, and mostpreferably Li. M is preferably Si, Ge or Sn, more preferably Si or Ge,and most preferably Si. X is preferably Cl, Br or I, more preferably Clor Br, and most preferably Cl. OR³ is preferably an alkoxy group havingfrom 1 to 4 carbon atoms, more preferably from 1 to 3 carbons, and mostpreferably 2 carbons (ethoxy). Also, “m” is preferably 3 or 4, whereas“n” is preferably 0 or 1.

[0086] R¹ and R² are independently preferably partially or fullyfluorinated (though not necessarily as can be seen in prior examples)organic groups such as an aryl group (by aryl group we mean any organicgroup having a ring structure) though preferably a five or six carbonring that is unsubstituted or substituted. For a six carbon ringstructure, 1, 2 or 3 substituents can be bound to the ring, whichsubstituents can be actively bound to the ring via a variation on theMethod C set forth above (to be described further below). Thesubstituents can be alkyl groups of any desired length, straight orbranched chain, preferably fluorinated, and preferably having from 1 to4 carbon atoms. Or the substituents on the ring structure can comprise aC═C double bond and be an alkenyl group (by alkenyl group we mean anyorganic group with a C═C double bond) such as an acrylate, vinyl orallyl group. A fluorinated vinyl, methyl or ethyl group on a fluorinatedphenyl group are examples. Or, the aryl group could be a multi ringstructure (e.g. perfluoronaphthalene or a biphenyl group). Or R¹ and R²could independently be an alkenyl group such as a vinyl or longer chaingroup having a C═C double bond, or a group having other types of doublebonds (e.g C═O double bonds or both C═C and C═O double bonds) such asacrylate and methacrylate groups. R¹ and R² could also be an alkynylgroup (by alkynyl group we mean any organic group with a carbon-carbontriple bond) as mentioned previously, as well as an alkyl group. If analkyl group (by alkyl group we mean a carbon chain of any length),preferably the carbon chain is from 1 to 14, and more preferably from 4to 8. Perfluorinated alkyl groups from 1 to 8 carbons can be used, aswell as fluorinated (e.g. partially fluorinated) groups longer than 8carbons. All the organic groups above could be deuterated in stead offluorinated (or partially deuterated and partially fluorinated), thoughfully or partially fluorinated (particularly fully fluorinated) ispreferred.

[0087] In Method C set forth above, an organic (or hybrid) group “R”(e.g. R2) becomes bound to a group 3-6 or 13-16 element “M” by replacinga halogen “X” bound to “M” via the specified reaction. In an alternativeto this method (Method D), an organic (or hybrid) group “R” (e.g. R1)comprises the halogen “X”—preferably Cl or Br (rather than “X” beingbound to “M”). Thus when the reaction is performed, R2 replaces X boundto R1, such that R2 becomes bound to R1 (which is in turn bound to M).Preferably the other groups bound to M are alkoxy groups (OR3) or otherorganic groups. More particularly, such a method comprises providing acompound X_(a)R¹MOR³ ₂R⁴ where a is from 1 to 3, X is a halogen(s) boundto R¹, R1 is an organic group (preferably an aryl, alkyl, alkenyl oralkynyl—more preferably an alkyl or aryl group), OR³ is an alkoxy, andR⁴ is either an additional alkoxy group or an additional organic group(selected from aryl, alkyl, alkenyl or alkynyl), and reacting thiscompound with R²M¹ where M¹ is selected from group 1 of the periodictable and R² is an organic group preferably selected from aryl, alkyl,alkenyl and alkynyl, etc., so as to form R² _(a)R¹MOR³ ₂R⁴.

[0088] In one embodiment, R⁴ is an alkoxy group the same as OR³, suchthat the method comprises reacting X_(a)R¹MOR³ ₃ with R²M¹ to form R²_(a)R¹MOR³ ₃ (where R¹ and OR³ are bound to M and R² is bound to R¹. Inanother embodiment, R⁴ is an organic group selected from aryl, alkyl,alkenyl and alkynyl. Preferably OR³ is a methoxy, ethoxy or propoxy, R¹is an aryl or alkyl (straight or branched chain) having from 1 to 14carbons, and R² is an aryl, alkyl, alkenyl or alkynyl, where a=1 or 2 ifR¹ is an alkyl and a=1, 2 or 3 if R¹ is an aryl group. R² can be anepoxy, acrylate, methacrylate, vinyl, allyl or other group capable ofcross linking when exposed to an electron beam or in the presence of aphotoinitiator and electromagnetic energy (e.g. UV light).

Example A Forming a Compound I or IV via Method D

1. 1,4-Br₂C₆F₄+Mg+Si(OEt)₄→Br(C₆F₄)Si(OEt)₃

2. Br(C₆F₄)Si(OEt)₃+CF₂═CFLi→(CF₂═CF)(C₆F₄)Si(OEt)₃

[0089]

[0090] 250 g (0.812 mol) 1,4-dibromotetrafluorobenzene, 21.709 g (0.8932mol) magnesium powder, small amount of iodine (15 crystals) and 181 mL(0.812 mol, 169.164 g) tetraethoxysilane were mixed together at roomtemperature and diethylether was added dropwise to the vigorouslystirred solution until an exothermic reaction was observed (˜250 mL).After stirring at room temperature for 16 h diethylether was evaporated.An excess of n-heptane (˜600 mL) was added to precipitate the magnesiumsalts. Solution was filtrated and evaporated to dryness. The residue wasfractionally distilled under reduced pressure to yield4-bromotetrafluorophenyltriethoxysilane.

[0091] 78.246 g (0.200 mol) 4-bromotetrafluorophenyltriethoxysilane inEt₂O is slowly added to solution of CF₂═CF—Li (0.200 mol, 17.592 g,prepared in situ) in Et₂O at −78° C. Reaction mixture is stirredovernight while it will slowly warm to room temperature. LiBr is removedby filtration and the product, 4-triethoxysilylperfluorostyrene,purified by distillation.

[0092] 117.704 g (0.300 mol) 4-triethoxysilylperfluorostyrene, 131 mL(1.800 mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol) pyridiniumhydrochloride were refluxed and stirred for 16 h Excess of SOCl₂ wasevaporated and 4-trichlorosilyl-perfluorostyrene isolated byvacuum-distillation.

[0093] The above example could be modified where 2 or 3 halogens (inthis case Br) are bound to the phenyl group so as to result in multiplevinyl substituents. Also, the phenyl group could be another organicgroup such as an straight or branched chain alkyl group, a multi ringaryl group, etc., whereas the vinyl group could be any suitable organicgroup capable of binding to a group I element (in the above example Li)and replacing the halogen (in the above example Br). Examples other thanvinyl include methyl, ethyl, propyl, phenyl, epoxy and acrylate.

Example B Forming a Compound I via Method D

CF₂Cl—C(═O)—ONa+ClSi(OEt)₃→CF₂Cl—C(═O)—O—Si(OEt)₃+NaCl

CF₂═CF—Li+CF₂Cl—C(═O)—O—Si(OEt)₃→CF₂═CF—CF₂—C(═O)—O—Si(OEt)₃+LiCl

[0094] 15.246 g (0.10 mol) sodium chlorodifluoroacetate, is dissolved to100 mL Et₂O and cooled to −70° C. 19.7 mL (0.10 mol, 19.872 g)chlorotriethoxysilane in Et₂O (50 mL) was added dropwise to reactionsolution. The solution was stirred for over night allowing it to warm upto room temperature. NaCl is removed by filtration and solutionevaporated to dryness to result clear colourless liquid,chlorodifluoroacetic acid, triethoxysilyl ester.

[0095] 29.27 g (0.10 mol) chlorodifluoroacetic acid, triethoxysilylester, is dissolved to 100 mL Et₂O and slowly added to solution ofCF₂═CF—Li (0.10 mol, 8.796 g, prepared in situ) in Et₂O at −78° C.Reaction mixture is stirred overnight allowing it slowly warm to roomtemperature. LiCl is removed by filtration and solution evaporated todryness to result yellow liquid, crude perfluoro-3-butene acid,triethoxysilyl ester.

Example C Forming a Compound I or IV via Method D

Br(C₆F₄)Si(OEt)₃+C₆F₅—Li→C₆F₅—C₆F₄—Si(OEt)₃+LBr

[0096] 78.246 g (0.200 mol) 4-bromotetrafluorophenyltriethoxysilane inEt₂O is slowly added to solution of C₆F₅—Li (0.200 mol, 34.80 g,prepared in situ) in Et₂O at −78° C. Reaction mixture is stirredovernight while it will slowly warm to room temperature. LiBr is removedby filtration and the product, perfluorobiphenyltriethoxysilane,purified by distillation.

[0097] 143.516 g (0.300 mol) perfluorobiphenyltriethoxysilane, 131 mL(1.800 mol. 214.1 g) thionylchloride and 4.51 g (0.039 mol) pyridiniumhydrochloride were refluxed and stirred for 16 h. Excess of SOCl₂ wasevaporated and perfluorobiphenyltrichlorosilane isolated byvacuum-distillation.

Example D Forming a Compound I or IV via Method D

1,4-Br₂C₄F₈+Mg+Si(OEt)₄→Br(CF₂)₄Si(OEt)₃

Br(CF₂)₄Si(OEt)₃+CF₂═CFLi→CF₂═CF—(CF₂)₄—Si(OEt)₃

[0098]

[0099] 143.94 g (0.40 mol) 1,4-dibromooctafluorobutane, 10.69 g (0.44mol) magnesium powder, small amount of iodine (15 crystals) and 88 mL(0.40 mol, 82.42 g) tetraethoxysilane were mixed together at roomtemperature and diethylether was added dropwise to the vigorouslystirred solution until an exothermic reaction was observed (˜200 mL).After stirring at room temperature for 16 h diethylether was evaporated.An excess of n-heptane (˜400 mL) was added to precipitate the magnesiumsalts. Solution was filtrated and evaporated to dryness. The residue wasfractionally distilled under reduced pressure to yield4-bromooctafluorobutanetriethoxysilane.

[0100] 88.641 g (0.200 mol) 4-bromooctafluorobutanetriethoxysilane inEt₂O is slowly added to solution of CF₂═CF—Li (0.200 mol, 17.592 g,prepared in situ) in Et₂O at −78° C. Reaction mixture is stirredovernight while it will slowly warm to room temperature. LiBr is removedby filtration and the product, perfluoro-1-hexenetriethoxysilane,purified by distillation.

[0101] 133.295 g (0.300 mol) perfluoro-1-hexenetriethoxysilane, 131 mL(1.800 mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol) pyridiniumhydrochloride were refluxed and stirred for 16 h. Excess of SOCl₂ wasevaporated and perfluoro-1-hexenetrichlorosilane isolated byvacuum-distillation.

[0102] In the above “Method D” examples, R¹, R², R³ and R⁴ arepreferably partially or fully fluorinated.

[0103] Hydrolysis and Condensation of the Compound(s):

[0104] Compounds IV, VII and IX have organic (or hybrid) R group(s) andhalogen(s) (preferably Br or Cl) bound to M (selected from groups 3-6 or13-16—preferably group 14)). These compounds can be hydrolyzed alone orin any combination to result in a material having a -M-O-M-O- backbonewith R groups bound to the backbone, and that preferably has a molecularweight of from 500 to 10,000 (more preferably from 1000 to 5000). In oneembodiment, a compound selected from Compound IV is hydrolyzed withanother compound selected from Compound IV. In another embodiment, asingle compound from Compound VII is hydrolyzed. Many other combinationsare possible, including: a) Compound IV+Compound VII; b) CompoundIV+Compound IV+Compound IV; c) Compound VII+Compound VII; d) CompoundIV+Compound VII+Compound IX; e) Compound IV+Compound IV+Compound IX; f)Compound VII+Compound IX, etc. Any other combinations, in any desiredratio, can be used for the hydrolysis and eventual deposition.

[0105] Hydrolysis Example 1—Compound IV+Compound IV:

[0106] If one of the compounds to be hydrolyzed and condensed ispentafluorophenyltrichlorosilane, this can be prepared as in the methodsset forth above, by:

C₆F₅Br+Mg+excess Si(OEt)₄→C₆F₅Si(OEt)₃+(C₆F₅)₂Si(OEt)₂

C₆F₅Si(OEt)₃+SOCl₂+py.HCl→C₆F₅SiCl₃

[0107] 100 mL (0.8021 mol, 198.088 g) pentafluorobromobenzene, 24.90 g(1.024 mol) magnesium powder and 716 mL (3.2084 mol, 668.403 g)tetraethoxysilane are mixed together at room temperature anddiethylether is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (˜200 mL). After stirring at 35° C.for 16 h the mixture is cooled to room temperature and diethyletherevaporated. An excess of n-heptane (˜500 mL) is added to precipitate themagnesium salts. Solution is filtrated and evaporated to dryness. Theresidue is fractionally distilled under reduced pressure to yieldpentafluorophenyltriethoxysilane.

[0108] 100 mL (0.375 mol, 124.0 g) pentafluorophenyltriethoxysilane, 167mL (2.29 mol. 272.0 g) thionylchloride and 5.63 g (0.0487 mol)pyridinium hydrochloride are refluxed and stirred for 24 h. Excess ofSOCl₂ is evaporated and pentafluorophenyltrichlorosilane

[0109] isolated by vacuum-distillation.

[0110] If a second of the compounds to be hydrolyzed and condensed istrifluorovinyltrichlorosilane, this can be prepared by:

[0111] 119 mL (0.155 mol) sec-butyllithium (1.3 M solution incyclohexane) is added under argon with stirring to 18.053 g (0.155 mol)chlorotrifluoroethylene

[0112] dissolved in Et₂O at −80° C. After the addition is complete thereaction mixture is stirred for 15 min to yieldlithiumtrifluoroethylene.

[0113] 30.80 g (0.155 mol) ClSi(OEt)₃ in Et₂O is slowly added tosolution of CF₂═CF—Li (0.155 mol, 13.633g, prepared in situ) in Et₂O at−78° C. Reaction mixture is stirred overnight while it will slowly warmto room temperature. LiCl is removed by filtration and the product,trifluorovinyltriethoxysilane,

[0114] is isolated by distillation.

[0115] 24.4 g (0.100 mol) trifluorovinyltriethoxysilane, 44 mL (0.60mol, 71.4 g) thionylchloride and 0.497 g (0.0045 mol) pyridiniumhydrochloride are refluxed and stirred for 24 h. Excess of SOCl₂isevaporated and trifluorovinyltrichlorosilane

[0116] is purified by distillation.

[0117] Then, to a solution of trifluorovinyltrichlorosilane andpentafluorophenyltrichlorosilane at a molar ratio 1:1 in dehydratedtetrahydrofuran, is added dropwise a stoichiometric amount of water(e.g. H2O or D2O) in THF at 0° C. (nonstoichiometric amounts, higher orlower, can also be used). After stirring for 1 hour, the solution isneutralized with 3 equivalents of sodium hydrogencarbonate. Afterconfirming the completion of generation of carbonic acid gas from thereaction solution, the solution is filtered and volatile compounds areremoved by vacuum evaporation to obtain colorless, transparent viscousliquid, poly(pentafluorophenyltrifluorovinylsiloxane), in a threedimensional network of alternating silicon and oxygen atoms.

[0118] The above is but one example of a method comprising: reacting acompound of the general formula R1MX3₃ with a compound of the generalformula R2MX3₃ where R1 is selected from alkyl, alkenyl, aryl andalkynyl, R2 is selected from alkenyl, aryl or alkynyl, M is an elementselected from groups 3-6 or 13-16 though preferably from group 14 of theperiodic table, and X3 is a halogen; with H2O or D2O; so as to form acompound having a molecular weight of from 500 to 10,000 with a-M-O-M-O- backbone with R1 and R2 substituents on each M.

[0119] In the hydrolysis example above, silicon atoms of the network aremodified by pentafluorophenyl and trifluorovinyl groups in anapproximate ratio 1:1. Of course other ratios are possible dependingupon the ratio of starting materials, and, of course, other threedimensional networks can be achieved by having other (or additional)starting materials selected from Compound IV, VII and IX, along withother hydrolyzable materials. An alternate example is a methodcomprising: reacting a compound of the general formula R1R2MX3₂ where R1is selected from alkyl alkenyl, aryl and alkynyl, R2 is selected fromalkenyl, aryl or alkynyl, M is an element selected from group 14 of theperiodic table, and X3 is a halogen; with D2O; so as to form a compoundhaving a molecular weight of from 500 to 10,000 with a -M-O-M-O-backbone with R1 and R2 substituents on each M.

[0120] Also, though “M” in the above hydrolysis example is silicon, itis possible to have materials with other M groups, or “dope” one or moresilanes to be hydrolyzed with a lesser amount of a compound having adifferent M group such as germanium (or boron, aluminum, selenium,etc.).

[0121] Deposition of the Hydrolyzed and Condensed Material:

[0122] The material formed as above preferably has a molecular weightbetween 500 and 10,000, more preferably between 1000 and 5000. Othermolecular weights are possible within the scope of the invention,however a weight between 1000 and 5000 provides the best properties fordepositing the material on a substrate. The substrate can be anysuitable substrate, such as any article of manufacture that couldbenefit from a hydrophobic and/or transparent layer or coating. In thefields of electronics and optical communications, the material could bedeposited as a final passivation layer, as a glob top coating, as anunderfill in a flip chip process, as a hermetic packaging layer, etc.Because the material can be patterned as will be discussed furtherbelow, the material could be deposited on a substrate (e.g. a glass,quartz, silicon or other wafer) as a buffer/cladding, waveguide/core orother layer within a waveguide or other optoelectronic/photonic device.

[0123] In general, the siloxane oligomer having the molecular weight asset forth above is mixed with a suitable solvent and deposited. If thematerial is to be patterned by exposure to electromagnetic radiation(e.g. UV light) then a photoinitiator can be mixed into the materialalong with the solvent. There are many suitable types of photoinitiatorsthat could be used, such as Irgacure 184, Irgacure 500, Irgacure 784,Irgacure 819, Irgacure 1300, Irgacure 1800, Darocure 1173 or Darocure4265. The initiator could be highly fluorinated, such as1,4-bis(pentafluorobenzoyl)benzene or Rhodosil 2074 photoinitiator.Also, thermal initiators can be applied for thermal crosslinking oforganic carbon double bond moieties, such as with Benzoyl peroxide,2,2′-Azobisisobutyronitrile, or tert-Butyl hydroperoxide.

Deposition Example 1

[0124] Add 10 w-% of methyl isobutyl ketone and 2 w-% of Irgacure 819photoinitiator to result in the formation of a spin-coatable andphoto-sensitive material. The material is deposited by spin coating,spray coating, dip coating, etc. onto a substrate or other article ofmanufacture. As mentioned herein, many other organic groups can be usedin place of the above groups, though preferably one of the groups in oneof the compounds is capable of cross linking when exposed toelectromagnetic energy (or an electron beam)—e.g. an organic group witha ring structure (e.g. an epoxy) or a double bond (e.g. vinyl, allyl,acrylate, etc.).

[0125] Forming a Waveguide:

[0126] One use of the material set forth above is as a layer within awaveguide. Though the waveguide could be a fiber optic waveguide (withsubstantially circular cross section) the example below is in relationto a planar waveguide. On a substrate (PCB, IC, silicon, glass or quartzwafer, etc.) is deposited a lower cladding layer. (A buffer layer canfirst be deposited if desired.) The cladding layer is made by formingCompounds IV, VII and/or IX and hydrolyzing such compound(s), followedby mixing the hydrolyzed material with a solvent and thermal initiatorand then depositing onto the substrate. After deposition, the claddinglayer can be fully or partially baked (or exposed to UV light if aphotoinitiator is used in place of the thermal initiator) to solidifythe cladding. On the cladding layer is deposited a core layer that ismade and deposited as above, except with a different ratio of compoundsor different compounds that are hydrolyzed/condensed to form thematerial ready for deposition. By modifying the hydrolysable compoundsand/or ratios of compounds in the core layer vs. those in the claddinglayer, a different index of refraction is achieved. A developer (e.g.e.g. methanol ethanol, propanol, acetone, methyl isobutyl ketone,tetrahydrofuran, Dow Chemical DS2100, Dow Chemical DS3000, etc.) is thenapplied to remove unexposed material. In this way, a core for thewaveguide is formed. Then an upper cladding layer is made and depositedin the same way as the lower cladding layer. Though in this example themask is a binary mask (the material is either fully exposed or notexposed to electromagnetic radiation), it is also possible to providepartial exposure (e.g. in a continuum from full exposure to a low ornon-exposure level as in a gray scale mask). Such a gray scale exposurecan form a vertical taper in the waveguide when the developer isapplied.

[0127] This invention has been described in connection with thepreferred embodiments. Many variations of the above embodiments arecontemplated as being within the scope of the invention.

In the claims:
 1. A compound of the general formula R′MR⁴R⁵R⁶ where R¹is an aryl, alkyl, alkenyl, epoxy or alkynyl group, and where R¹ isfully or partially fluorinated, wherein M is selected from group 14 ofthe periodic table, wherein R⁴, R⁵ and R⁶ are independently an alkoxygroup, OR³, or a halogen group X, except, a) where R⁴, R⁵ and R⁶ areeach ethoxy, M is Si and R¹ is perfluorinated phenyl or perfluorinatedvinyl; b) where R⁴ is ethoxy, R⁵ and R⁶ are chlorine, M is Si, and R¹ isperfluorinated phenyl; or c) where R⁴, R⁵ and R⁶ are chlorine, M is Si,and R¹ is perfluorinated phenyl, perfluorinated methyl or perfluorinatedvinyl.
 2. The compound of claim 1, wherein X is Br or Cl.
 3. Thecompound of claim 1, wherein R1 is fully fluorinated.
 4. The compound ofclaim 3, wherein R1 is an alkenyl or alkynyl group.
 5. The compound ofclaim 1, wherein R1 is an alkyl group having from 1 to 14 carbons, vinylor allyl group.
 6. The compound of claim 1, wherein R1 is an alkenylgroup.
 7. The compound of claim 1, wherein R1 is a fully fluorinatedalkenyl group.
 8. The compound of claim 1, wherein R1 is an aryl grouphaving one or more rings, or an alkyl group having from 1 to 14 carbons.9. The compound of claim 1, wherein R1 is an alkynyl group.
 10. Thecompound of claim 1, wherein R4 is a halogen X and R5 and R6 areindependently alkoxy groups.
 11. The compound of claim 1, wherein R4 isan alkoxy group and R5 and R6 are independently halogen groups.
 12. Thecompound of claim 1, wherein R1 is a fully or partially fluorinatedphenyl group substituted with fully or partially fluorinated methyl,vinyl or ethyl groups.
 13. The compound of claim 1, wherein OR3 is C1-C4alkoxy.
 14. The compound of claim 1, wherein M is Si, Ge, Al or Sn. 15.The compound of claim 1, wherein X is Cl.
 16. The compound of claim 1,wherein X is Br.
 17. The compound of claim 1, wherein R4, R5 and R6 areeach a halogen X.
 18. The compound of claim 1, wherein R4, R5 and R6 areeach an alkoxy group OR3.
 19. The compound of claim 1, wherein R1 is aC2+straight chain or C3+branched chain.
 20. The compound of claim 1,wherein R1 is a perfluorinated organic group having an unsaturateddouble bond.
 21. The compound of claim 1, wherein R1 is an epoxy group.22. The compound of claim 1, wherein R1 an acrylate group.
 23. Thecompound of claim 22, wherein M is Si or Ge.
 24. The compound of claim1, wherein R1 is vinyl.
 25. The compound of claim 24, wherein R1 isfully fluorinated vinyl.
 26. The compound of claim 1, wherein R4, R5 andR6 are each methoxy or propoxy, M is Si and R1 is perfluorinated phenylor perfluorinated vinyl.
 27. The compound of claim 1, wherein R4 ismethoxy or propoxy, R5 and R6 are Cl, M is Si and R1 is perfluorinatedphenyl.
 28. The compound of claim 1, wherein R4, R5 and R6 are Cl, M isSi, and R1 is perfluorinated substituted phenyl or perfluorinated alkylhaving from 2 to 8 carbons.
 29. The compound of claim 28, wherein R1 isperfluorinated ethyl or propyl.
 30. The compound of claim 1, wherein OR3is methoxy or ethoxy.
 31. The compound of claim 1, wherein OR3 isethoxy.
 32. The compound of claim 1, wherein R1 is a fully or partiallyfluorinated single ring or polycyclic aromatic substituent.
 33. Thecompound of claim 32, wherein either R1 has one or two rings.
 34. Thecompound of claim 1, wherein M is Si.
 35. The compound of claim 1,wherein R1 is methyl.
 36. The compound of claim 1, wherein R1 is ethyl.37. The compound of claim 1, wherein R1 is propyl.
 38. A method formaking the compound R¹MR⁴R⁵R⁶ of claim 1, comprising: providing acompound MOR3_(q)X_(4−q) where M is an element selected from group 14 ofthe periodic table, OR3 is an alkoxy group, X is a halogen and q is 3 or4; reacting the compound MOR3_(q)X_(4−q) with either a) Mg and R1X2where X2 is Cl, Br or I and R1 is an alkyl, alkenyl, aryl or alkynylgroup, and q=4, or b) with R1M1 where R1 is an alkyl, alkenyl, aryl oralkynyl group and wherein R1 is fully or partially fluorinated and M1 isan element from group 1 of the periodic table, and q=3 or 4; so as toform R1MOR3₃, and wherein if R4, R5 or R6 is a halogen, further reactingR1MOR3₃ with a halogen or halogen compound so as to form R¹MR⁴R⁵R⁶. 39.A method for using the compound of claim 1, comprising: providing thecompound of claim 1; hydrolyzing the compound of claim 1 in the presenceof H2O or D2O with another compound having the formula R²MR⁴R⁵R⁶; so asto form a compound with an -M-O-M-O- backbone with at least R1 and R2groups bound thereto and having a molecular weight of from 500 to10,000.
 40. The method of claim 39, wherein the compound has a molecularweight of from 1500 to 5000.